Synthesis of Polymers >> Content Detail

Study Materials


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The readings consist of sections from the primary text, journal articles, and handouts. The readings should be completed before attending lecture. The sections given below come from the course required text.

Required Text

Amazon logo Odian, George. Principles of Polymerization. 4th ed. Hoboken, NJ: Wiley-Interscience, 2004. ISBN: 9780471274001.



Course Overview

Polymer Design and Synthesis

Reaction Types and Processes

Introduction to Step Growth

Sections 1-1 to 1-4.

"Examples of Common Functional Groups Used in Step Growth Polymerization" Handout.

Step Growth Polymerization

Molecular Weight (MW) Control

Molecular Weight Distribution (MWD) in Equilibrium Step Condensation Polymerizations

Interchange Reactions: Effects on Processing and Product

Application Example: Common Polyesters

Sections 2-1a, 2-4ab, 2-2abcd, especially 2-2ab.

Step Growth Polymerization

Types of Monomers

Kinetics and Equilibrium Considerations

Closed vs. Open Systems

Sections 2-6ab, 2-7abc, and 2-8defg.

Edlund, U., and A.-C. Albertsson. "Polyesters Based on Diacid Monomers." Advanced Drug Delivery Reviews 55 (2003): 585-609.

Ikada, Y., and Hideto Tsuji. "Biodegradable Polyesters for Medical and Ecological Applications." Macromolecular Rapid Communications 21, no. 3 (2000): 117-132.


Common Processing Approaches

Near-equilibrium vs. Far from Equilibrium

Homogeneous Solution and Bulk Polymerization

Section 2-8ab.

Erdmann, L., and K. E. Uhrich. "Synthesis and Degradation Characteristics of Salicylic Acid-Derived Poly(anhydride-esters)." Biomaterials 21 (2000): 1941-1946.


Interfacial Polymerizations

Application Examples: Polyamides

Section 2-8c.

Anderson, Daniel G., David M. Lynn, and Robert Langer. "Semi-Automated Synthesis and Screening of a Large Library of Degradable Cationic Polymers for Gene Delivery." Angew Chem Int Ed 42 (2003): 3153-3158.


Other Polymers of Interest Obtained by Step-Growth



Segmented and Block Copolymers from Step Condensation Methods

Sections 2-8defg and 2-13bc.

Crosslinking and Branching

Network Formation and Gelation

Carothers Equation: Pn Approach

Sections 2-9 and 2-10a.

Network Formation

Statistical Approach: Pw Approach

A Word on MWD for Nonlinear Polymerizations

Sections 2-10b, 2-11, and 2-12.

Step-by-Step Approaches I: Polypeptide Synthesis: Examples from Biology

Step-by-Step Approaches II: Dendrimers, Traditional Convergent and Divergent Routes

New "one-pot" Approaches to Hyperbranced Species

Section 9-13.

Fréchet, Jean M. "Dendrimers and Other Dendritic Macromolecules: From Building Blocks to Functional Assemblies in Nanoscience and Nanotechnology." J Polym Sci Part A: Polym Chem 41 (2003): 3713-3725.

Tomalia, Donald A., and Jean M. Fréchet. "Discovery of Dendrimers and Dendritic Polymers: A Brief Historical Perspective." J Polym Sci Part A: Polym Chem 40 (2002): 2719-2728.

van Hest, Jan C. M., and David A. Tirrell. "Protein-Based Materials, Toward a New Level of Structural Control." Chem Commun (2001): 1897-1904.

Free Radical Chain Polymerization
10Introduction to Radical Polymerization

Radical Polymerization

Homogeneous Reaction Rate Kinetics

Sections 3-1a and 3-3ab.

Free Radical Kinetic Chain Length


Chain Transfer


Sections 3-5ab, 3-6a, and 3-6c.

Thermodynamics of Free Radical Polymerizations

Ceiling T's

Tromsdorff Effect

Instantaneous Pn

Sections 3-9bc and 3-10.
14Processing Approaches: Emulsion Polymerization ProcessesAmazon logo Rempp, P., and Edward W. Merrill. "Emulsion and Suspension Polymerization." Chapter 12 in Polymer Synthesis. 2nd Revised ed. New York, NY: Hüthig and Wepf, 1991. ISBN: 9783857391149.

Processing Approaches: Suspension (Bead) Polymerization Processes

Polyvinyl Chloride Via Precipitation Polymerization

Polyethylene Via Radical Polymerization

Amazon logo Rempp, P., and Edward W. Merrill. "Emulsion and Suspension Polymerization." Chapter 12 in Polymer Synthesis. 2nd Revised ed. New York, NY: Hüthig and Wepf, 1991. ISBN: 9783857391149.

Ziegler-Natta Catalysis

Stereochemistry of Polymers

Sections 6-1, 6-2ad, 6-3ab, especially 6-3b-4.
17Stereoregular PolymerizationsSections 8-1, 8-4abc, and 8-4fg.
18Radical Copolymerization: Alternating to Block Copolymers

Hlatky, G. G. Page 246 in "Metallocene Catalysts for Olefin Polymerization: Annual Review for 1996." Coordination Chemistry Reviews 181, no. 1 (1999): 243-296.

Yanjarappa, M. J., and S. Sivaram. Pages 1350-1353, 1356, and 1364 in "Recent Developments in the Synthesis of Functional Poly(Olefin)s." Prog Polym Sci 27, no. 7 (2002): 1347-1398.

Ionic Polymerization

Metallocene Chemistry

Introduction to New Developments from Brookhart, et al.

Sections 5-1 and 5-3.

Introduction to Anionic Polymerization

Monomers Applicable to Anionic Methods

Kinetics of "Nonliving" Anionic Polymerization

Section 5-3e.

Living Anionic Polymerization

Effects of Initiator and Solvent

22Anionic Block CopolymerizationSection 5-4abcd.

Anionic Ring Opening Polymerization

End Group Functionalization

Telechelic Oligomers and Novel Architectures Using Coupling Techniques

Lazzari, Massimo, and M. Arturo López-Quintela. Pages 1583-1589 in "Block Copolymers as a Tool for Nanomaterial Fabrication." Adv Mater 15, no. 19 (October 2, 2003): 1583-1594.

Introduction to Cationic Polymerization, Monomers, Kinetics

Sections 5-2a1, 5-2a2, and 5-2b.

Cheng, J. Y., C. A. Ross, E. L. Thomas, H. I. Smith, and G. J. Vancso. "Fabrication of Nanostructures with Long-Range Order Using Block Copolymer Lithography." Appl Phys Lett 81, no. 19 (November 4, 2002): 3657-3659.

Hamley, I. W. "Nanotechnology with Soft Materials." Angew Chem Int Ed 42 (2003): 1692-1712.


"Living" Cationic Polymerizations

Examples of Cationic Polymerization, Isobutyl Rubber Synthesis, Polyvinyl Ethers


Anionic Ring Opening Polymerization

Cationic Ring Opening Polymerization

Other Ring Opening Polymerizations

27Polysiloxanes, Lactams, etc.
Polymer Functionalization and Modification

Introduction to Polymer Functionalization: Motivations, Yield, Crystallinity, Solubility Issues

Common Functionalization Approaches
Sections 9-1a to 9-1k.
29Functionalization Case Studies: Biomaterials Systems, Liquid Crystal (LC) PolymersSections 9-4, 9-5, and 9-6.
Less Traditional Approaches to Polymer Synthesis

Surface Functionalization of Polymers

Graft Copolymerization

Approaches to Making Comb and Graft Architectures

Grafting onto Existing Polymer Surfaces

Surface Engineering Using Graft Copolymers

Section 9-8.

"Living" Free Radical Approaches: Stable Free Radical Polymerization

Atom Transfer Radical Polymerization (ATRP)



RAFT and Other New Methods

Ring Opening Metathesis Polymerization (ROMP)

Coca, Simion, and Krzystof Matyjaszewski. "Block Copolymers by Transformation of 'Living' Carbocationic into 'Living' Radical Polymerization." Macromolecules 30 (1997): 2808-2810.

Davis, Kelly A., and Krzystof Matyjaszewski. Pages 1-13 in "Statistical, Gradient, Block, and Graft Copolymers by Controlled/Living Radical Polymerizations." Advances in Polymer Science 159 (2002): 1-169.

Patten, Timothy E., and Krzystof Matyjaszewski. "Atom Transfer Radical Polymerization and Synthesis of Polymeric Materials." Advanced Materials 10, no. 12 (1998): 901-915.

Pyun, Jeffrey, Shijun Jia, Tomasz Kowalewski, and Krzystof Matyjaszewski. "Synthesis and Surface Attachment of ABC Triblock Copolymers Containing Glassy and Rubbery Segments." Macromol Chem Phys 205 (2004): 411-417.



Oxidative Coupling

Electrochemical Polymerizations

Case Study: Electro-active Polymers

Grubbs, R. H., R. H. Friend, E. W. Meijer, R. W. Richards, and N. R. Cameron. "Jim Feast: A Career in Polymer Science." Polymer 46, no. 5 (February 14, 2005): 1427-1438.

Saunders, R. S., R. E. Cohen, and R. R. Schrock. "Synthesis and Characterization of Diblock Copolymer Films Containing Self-Assembled Polyacetylene Structures." Macromolecules 24, no. 20: 5599-5605.

34Inorganic Polymer Synthesis

Manners, Ian. "Poly (ferrocenylsilanes): Novel Organometallic Plastics." Chem Commun (1999): 857-865.

Wang, Xiao-Song, André Arsenault, Geoffrey A. Ozin, Mitchell A. Winnik, and Ian Manners. "Shell Cross-Linked Cylinders of Polyisoprene-b-ferrocenyldimethylsilane: Formation of Magnetic Ceramic Replicas and Microfluidic Channel Alignment and Patterning." J Am Chem Soc 125 (2003): 12686-12687.

Additional Reading

Photorefractive Polymers

Yu, L. P. "Lessons Learned From Research on Photorefractive Polymers and Molecular Materials." Journal of Polymer Science Part A-Polymer Chemistry 39, no. 15 (August 1, 2001): 2557-2564.

Bao, Z. N., and L. P. Yu. "Recent Progress in the Synthesis and Applications of Porphyrin-Containing Polymers as Electronic and Photonic Materials." Trends in Polymer Science 3, no. 5 (May 1995): 159-164.


Gleria, M., and R. De Jaeger. "Polyphosphazenes: A Review." New Aspects in Phosphorus Chemistry V Topics in Current Chemistry 250 (2005): 165-251.


Fujlki, M., J. R. Koe, K. Terao, T. Sato, A. Teramoto, and J. Watanabe. "Optically Active Polysilanes. Ten Years of Progress and New Polymer Twist for Nanoscience and Nanotechnology." Polymer Journal 35, no. 4 (2003): 297-344.

Tachibana, H., and Y. Tokura. "Optical-Properties of Polysilanes and Related Materials." Synthetic Metals 71, nos. 1-3 (April 1, 1995): 2005-2008.


Macromolecular Systems Via Secondary Bonding: Use of H-bonding and Ionic Charge to Build Structures

Concept of Self-Assembly - From Primary Structure to Complex Structure

Additional Reading

Hydrogen Bonding in Polymeric Structures

Kato, T., H. Kihara, S. Ujiie, T. Uryu, and J. M. J. Fréchet. "Structures and Properties of Supramolecular Liquid-Crystalline Side-Chain Polymers Built Through Intermolecular Hydrogen Bonds." Macromolecules 29, no. 27 (December 30, 1996): 8734-8739.

Alexander, C., C. P. Jariwala, C. M. Lee, and A. C. Griffin. "Self-Assembly of Main-Chain Liquid-Crystalline Polymers via Heteromeric Hydrogen Bonding." Macromolecular Symposia 77 (January 1994): 283-294.

Muller, M., A. Dardin, U. Seidel, V. Balsamo, B. Ivan, H. W. Spiess, and R. Stadler. "Junction Dynamics in Telechelic Hydrogen Bonded Polyisobutylene Networks." Macromolecules 29, no. 7 (March 25, 1996): 2577-2583.

2-Dimensional Polymers

Stupp, S. I., S. Son, H. C. Lin, and L. S. Li. "Synthesis of 2-Dimensional Polymers." Science 259, no. 5091 (January 1, 1993): 59-63.

Stupp, S. I., S. Son, L. S. Li, H. C. Lin, and M. Keser. "Bulk Synthesis of 2-Dimensional Polymers - The Molecular Recognition Approach." Journal of the American Chemical Society 117, no. 19 (May 17, 1995): 5212-5227.

Electrochemical Polymerization

Okahata, Y., and G. Enna. "Permeability-Controllable Membranes. 7. Electrochemical Responsive Gate Membranes of a Multibilayer Film Containing a Viologen Group as Redox Sites." Journal of Physical Chemistry 92, no. 15 (July 28, 1988): 4546-4551.

Self-Assembly of Viruses and Liquid Crystalline Polymers

Percec, V. "Self-Assembly of Viruses as Models for the Design of New Macromolecular and Supramolecular Architectures." Journal of Macromolecular Science-Pure and Applied Chemistry A33, no. 10 (1996): 1479-1496.

———. "Bioinspired Supramolecular Liquid Crystals." Philosophical Transactions of the Royal Society A-Mathematical Physical and Engineering Sciences 364, no. 1847 (October 15, 2006): 2709-2719.

Multilayer Assembly

Hammond, P. T. "Form and Function in Multilayer Assembly: New Applications at the Nanoscale." Advanced Materials 16, no. 15 (August 3, 2004): 1271-1293.


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